Detergent composition



United States Patent DETERGENT COMPOSITION Louis McDonald, Inyokern, Calif.

No Drawing. Application March 9, 1948, Serial No. 13,938

5 Claims. (Cl. 252-116) The present invention relates to detergent compositions and it particularly relates to foam free compositions having superior cleansing properties.

In using soap flakes or powders or synthetic detergent powders in washing machines, it has been found that the production of large amounts of suds not only causes slopping over of the washing fluid and the suds and considerable messiness around the machine and in the room or basement where the machine is kept, but also disadvantageously afiects the cleansing efiiciency obtained.

The suds remain in the machine, and particularly in and around crevices, even after several rinsings, and in case of hard water they cause formation and deposition of curd-like deposits of insoluble soaps both upon the clothes and in the interior of the machine and drain conduits leading therefrom.

It is among the objects of the present invention to prepare a novel detergent composition, particularly adapted for washing machines, having very high detergent properties without any appreciable suds formation.

Another object is to prepare a novel detergent composition made of relatively inexpensive raw materials which will not be disadvantageously alfected in its detergent properties by Widely varying temperatures and will not be decreased in its detergency by varying types of hardness in the water.

Still further objects and advantages will appear in the more detailed description set forth below, it being understood, however, that this more detailed description is given by way of illustration and explanation only and not by way of limitation, since various changes may be made therein by those skilled in the art Without departing from the scope and spirit of the present invention.

According to the preferred procedure of the present invention a large quantity of a synthetic non-soap organic detergent of the type of an ethylene oxide condensation product of a polyhydroxy-fatty acid mono ester is combined with a small amount of a Water insoluble plastic material of non-tacky nature or low tackiness.

The preferred plastic material is ethyl cellulose which has been dissolved in an organic solvent, and this solution is then emulsified in an aqueous medium with a plasticizer. Such plasticizer is desirably a partly fatty acid esterified polyhydric alcohol, the preferred plasticizers being Glycerol monostearate Mannide oleate Mannitan oleate Diglycol stearate Diglycol oleate The preferred ethyl cellulose is of the type having 2.5 ethoxy groups per glucose residue and a 150 centipoise viscosity rating.

Although the above composition may be used by itself, it is preferably combined with a major proportion of a soap, a sodium or potassium oleate, stearate or palmitate soap being preferred.

An unusually effective detergent composition is made by combining a relatively large quantity (for example 50% to 95%) of ammonium, sodium, potassium or alkanolamine stearate, palmitate, laurate, oleate, ricinoleate, abietate, linoleate, or salts of mixed fattV acids "derived from splitting of various animal, vegetable and marine oils. waxes and fats, with a relatively small amount (5% {to 25%) of an ethylene oxide condensationproduct oxide shown may vary from 2 to 12 in -C2H4O groups.

of an anhydro-polyhydroxy compound esterified with high molecular weight fatty acids.

The fatty acids used for esterification may be the same as those included in the soap or may be derived from greases, such as garbage greases, animal bone grease and slaughter house rendering grease. The fatty acids should generally have from 12 to 22 carbon atoms.

The polyhydroxy compounds condensed with ethylene oxide desirably have four or more hydroxy groups, such as sorbitol, mannitol, mannitan and sorbitan. The grease fatty acids are usually low titre fatty acids, for example giggigg a titre of 25 C. to C. and desirably about The preferred esterified synthetic non-soap organic detergent compound, known as Detergent 1226 or Renex in the trade, is an anhydro-polyhydroxy compound fatty acid ester having a ring structure and the following general where n is preferably 4 but may range from 2 to 12; and x is 9 to 20 depending upon the fatty acid used. This compound may be described as a C9 to C20 fatty acid esterified polyhydroxy alcohol-ethylene oxide condensation product and the specific example is the detergent known as 1226 or Renex. As indicated, the ethylene In detergent 1226, the fatty acids are mixture of saturated and unsaturated acids, such as oleic, stearic, palmitic and myristic. Simular detergents are known as Tween which is sorbitan monostearate ethylene oxide condensate and Tween 20 which is sorbitan laurate ethylene oxide condensate.

It has also been found desirable to include in the composition in lieu of a part of the polyethylene glycol ester 21 small amount-from 1% to 5% by weightof anionic organic detergents, such as normal polymerized alkyl sulphonates, for example dibutyl naphthalene sodium sulpho nates, alkyl esters of di-basic carboxylic acids, for example disodium mono-lauryl ester of sulfonsuccinic acid, or sodium fatty alcohol sulfates for example sodium lauryl sulfates or aryl polyethylene oxide sodium sulphates.

These detergent materials should preferably be of anionic nature.

In general the synthetic non-soap detergents present in the detergent composition should have two components:

(A) A foaming detergent generally of anionic nature including a fatty alcohol (12 to 18 carbon atoms) sulphate or sulphonate known in the trade as Gardinol or Avirol; amido-high alkyl sulphates or collamids known in the trade as Igepon T; alkyl substituted aryl sulphonates known in the trade as Nacconol; or polysulphonates of aromatic polyalkylene ether sulphates, such as Triton 770. Soap may replace part or all of these foaming nonsoap detergents.

(B) Foam depressing detergent including less preferably sulphonated or sulphated oils, waxes or tallows and most desirably partially fatty acid esterified polyhydroxy aliphatic ethylene oxide condensates known in the trade as Tween, and particularly the detergent known as 1226. Non-ionic detergents are preferably not included when they have foaming characteristics. The foam depressing detergents are usually non-ionic.

The foaming or anionic non-soap synthetic detergents have a temperature stabilizing effect and prevent decrease in solubility of the non-foaming detergent or salting out thereof at high temperatures in the order of F. to 220 F. when the detergent compositions are used in household or industrial washing machines, or in otherconnections.

The preferred anionic detergents are .most 'widely.

known by their trade-names as Triton 770, Triton 720, Arctic Syntex M, Igepon T and Nacconol.

Igepon T has the general formula:

RCONH--CHzCHzSO3Na where R is an alkyl group of 12 to 22 carbon atoms. In Igepon T the alkyl group is usually C1'7H33.

Triton 770 is a sulphonate of an aromatic polyalkylene ether sulfate having the general formula:

Aryl' JO (CnHZnO) x-CnHZnSOBH Arctic Synthex M has the general formula:

CH(CH2)12 m 20 COOCHCH(OH)CH2SO4Na Nacconol is a phenyl keryl or cetyl sodium sulphonate.

The ethyl cellulose ether used should have at least 2 and desirably less than 4 ethoxy groups per glucose residue. Preferably there should be 2 /2 to 2 5 ethoxy groups per glucose residue. Less preferably, the ethyl cellulose may be replaced by intermediate water insoluble, organic solvent soluble urea-formaldehyde, vinyl alcohol, vinyl chloride, vinylidene chloride, styrene, methacrylate, butadiene, or alkyd resinous condensation products.

For example, the water insoluble ethyl cellulose containing 2 /2 ethoxy groups per glucose residue or per six carbon chain is dissolved in equal parts of an organic solvent, such as a toluene-ethanol mixture, and this combination is then emulsified in about an equal weight of water containing plasticizers, such as sorbitan or mannitan oleate or riccinoleate.

The emulsification may be obtained by running the product through a colloid mill or homogenizer. After emulsification the toluene and alcohol may be partly or largely removed by low pressure distillation. In this way sufiicient organic solvent may be removed to give the same weight of ethyl cellulose dispersion and the same percentage strength of ethyl cellulose in the water emulsion as in the organic solvent solution.

The preferred formulation has as the principal ingredients:

(I) A sodium soap, such as a stearate or palrnitate, 70%

(II) An ethylene oxide condensation product of sorbitol, mannitol, sorbitan, or mannitan combined or esterified with long chain fatty acids, having 12 to 22 carbon atoms 10% to 25%; and

(III) Water insoluble ethyl cellulose water emulsion,

The preferred formulation may also include:

Example I To give a typical example:

Parts by weight (a) Fatty acid (C9 to C20) ester of ethylene oxide 1)r21ggr)1sation product of sorbitol or mannitol (b) Sodium stearate or palmitate 80 (c) Emulsified ethyl cellulose (25% ethyl cellulose,

25% toluene-alcohol solvent, 50% water) /2 Components (a) and (c) are first thoroughly combined and are then added to a soap kettle containing molten soap of 65% strength35% water, at a temperature of 140 F. to 180 F. and preferably 160 F. After crutching the mixture thoroughly, it is poured out onto rolls and formed into wet ribbons and then dried in a conveyor at 160 F. for minutes. The ribbons may be flaked or milled with various sodium salts such as tetrasodium pyrophosphate, sodium carbonate, trisodium phosphate and sodium metasilicate.

The resultant material is a sudless or foamless detergent of high detergent powers which will not be disadvantageously affected by varying temperatures and hard wa er.

4 Example II As another typical example the following may be used Per cent Soda soap 50 to 80 Foaming synthetic detergent, such as Triton 770 described above /2 to2 Non-foaming synthetic detergent such as the formula Detergent 1226 set forth above--- 10 to 50 Preferably 30 Water insoluble ethyl cellulose emulsion, such as the emulsion set forth above /1 to2 The non-foaming synthetic non-soap organic detergent not only assures repression of the foam of the soap and foaming synthetic non-soap organic detergent but also stabilizes the detergent properties of the composition from room temperature up to 160 to 200 F.

In preparing the above, the synthetic detergent 1226 with or without inclusion of foaming synthetic detergent is warmed to 160 F. in jacketted mixing kettle or crutcher. Then the ethyl cellulose emulsion is added and the combination is crutched for about 15 minutes at 160 F. Alkali metal carbonates, phosphates and silicates may be added after the ethyl cellulose, as may also the protective colloids. The product may be spray dried, conveyor dried or granulated in a graining machine.

The various water dispersible thickening agents or protective colloids which may be used are gum acacia, gum tragacanth, gum arabic, agar agar, pectin, dextrin, British gum, gum shiraz or water soluble cellulose derivatives, such as methyl celluloses. Methyl celluloses in contrast with water insoluble ethyl cellulose are usually water soluble. The preferred methyl cellulose has a solubility of 64 grams per 100 ml. at 25 C. with 2.6 methoxy groups per 12 carbon cellulose unit.

To give several. other examples:

Example III Per cent Emulsified ethyl cellulose yi to2 Detergent 1226 30 Soda soap Balance Example IV Per cent 40 Emulsified ethyl cellulose to 2 Detergent 1226 Balance Example V Per cent Emulsified ethyl cellulose A to 2 Detergent 1226 25 Sodium pyrophosphate 10 to 15 Soda soap Balance Example VI 5 Per cent Emulsified ethyl cellulose A to 2 Sodium carbonate mm 20 Detergent 1226 Balance Example VII Per cent Emulsified ethyl cellulose /2 Triton 770 1 Detergent 1226 Balance Example VIII Per cent Emulsified ethyl cellulose /2 Triton 770 1 Soda ash 15 Detergent 1226 Balance Example IX Per cent Emulsified ethyl cellulose ,5 Triton 770 1 Corn starch 25 Detergent 1226 Balance Example X Per cent Emulsified ethyl cellulose A Triton 77 1 Sodium pyrophosphate 10 Methyl cellulose 25 i Detergent 1226 Balance Example XI Per cent Emulsified ethyl cellulose Vs Triton 770 1 Sodium silicate Starch Carboxy-methyl cellulose 7 Detergent 1226 Balance Where some foam is desired or where the washing is done in salt or hard Water, part or all of the foam represser detergent that is the Tween or detergent 1226 may be replaced by Triton X-100, Igepal C. A. or any ethylene oxide condensate. These detergents in combination with Triton 770 or another aryl alkyl ether will function over a wide range of pH and will thoroughly disperse any curd due to electrolyte being present or calcium or magnesium precipitates of fatty acid salts. Preferential leaching out of the non-ionic detergent Triton X-l00 will also be prevented.

As a typical example:

Example XII Per cent Triton X100 (non-ionic) Triton 770 4 to 5 Emulsified ethyl cellulose /2 Soda soap Balance HOCH2(CH2OCH2) nCHOH where n is 8 to 90 ethylene oxide groups. The commercially available material contains approximately 12 ethylene oxide groups.

Igepal CA is identified by the general formula:

where n represents 1 to 20 ethylene oxide groups. The preferred commercial material contains about 6 ethylene oxide groups.

Resins such as water insoluble low polymerized vinyl acetate or polyvinyl alcohols may be substituted for part or all of the ethyl cellulose, if tackiness is avoided, in the above formulations.

The above detergent compositions have most satisfactory micelle formation which is required to achieve a high etficiency detergent. The micelle formation will be largely controlled by the ethyl cellulose emulsion inclusion. upwards of 100 molecules are the efiective cleansing agents.

For example synthetic non-soap detergents are poor cleansing agents since they do not associate into micelles readily and it usually requires the addition of as much as of a salt such as sodium sulphate to achieve such micelle formation.

Where soap is combined with such a combination of a synthetic non-soap detergent and a sodium salt, the salt will prevent the soap from being an effective detergent. The ethyl cellulose on the other hand assures effective detergency and micelle formation of both the synthetic non-soap detergent and the soap.

The micelles which are each combination of The various synthetic organic non-soap detergents I which may be used according to the present invention may be classified and tabulated as follows:

I. Non-ionic foam depressers. These are Tween and 1226 and are in general anhydrohexitol (sorbitol or mannitol) fatty acid partial ester ether condensates in which one hydroxy of the hexitol is esterified with a fatty acid and 30% the hydroxy groups are condensed with ethylene oxide. Generally there are four C2H4O groups in the chain and a --C2H4OH- group at the terminal end of the poly-ether chain. These depressers are used to reduce or eliminate foam in Washing machine compositions.

II. Anionic high foamers, useful in maintaining the non-ionic foam depressers or any anionic high foamers in solution at high temperatures of 160 F. to 220 F. These compounds are:

(a) Arctic Syntex M, a sulphated ester such as lauryl sulfoacetate.

(b) Nacconol, a phenyl keryl sulphonate.

(c) Triton 770, a phenyl polyethylene oxide sulphate.

(d) Igepon T, a collamid sulphonate.

(e) Triton 720, a phenyl polyethylene oxide sulphonate.

(1) MP 198, a keryl sulphonate.

(g) Ultrawet, a keryl sulphonate.

(h) Arctic Syntex T, a sulphonated collamid.

III. Non-ionic high foamers useful in salt or hard water soaps and detergents.

(j)d Triton X100, a polyether alcohol ethylene oxide conensate.

(k) Triton NE, a 30% solution of Triton X100.

(1) Igepal CA, same as Triton X100.

Nekal NS, tri (Z-ethyl butyl) sodium sulphotricarballylate Aerosol OT, sodium dioctyl sulphosuccinate Tergitol, higher secondary alcohol sulphates, particularly secondary octyl alcohol sodium sulfate.

Components I and II are combinedwith or without soap to form a sudless detergent, while a combination of components II and IIIwith or without soap-forms a salt water or hard water detergent. The ethyl cellulose addition in either case regulates and retards the rate of solution so that the various detergents I, II and IIIand the soap if also present-will also dissolve at a uniform rate and give rise to proper micelle formation and high detergent efliciency.

In the sudless detergent useful in household and industrial washing machines, the non-ionic foam depresser, namely Atlas 1226 is desirably used in quantities of 20 to 30% as compared to a soap content of about 80% to 70%. The ethyl cellulose equalizes the rate of solu-v tion of 1226 and soap and increases micelle formation. This sudless detergent is effectively used in salt or hard water. 7

For manual use with salt or hard water, it is usually desirable to use a sudsing composition containing 5 to 7% of Triton X100, Triton NE or Igepal C. A. together with about 93 to 95% of soda soap. Here again the 5% colloided ethyl cellulose make an effective detergent out of a composition which would be an ineffective detergent.

To obtain a slow dissolving floating soap, or to obtain a slow dissolving soap for combination with paper iron Wool, pumice or other insoluble to 1% of the colloided ethyl cellulose may be used with the soap or soapless detergent or combination of both.

With polymerized vinyl acetate as a hinder or solution retarder 25 parts of the vinyl acetate are dissolved in a mixture of 50 parts of cyclohexanone and 50 parts of acetone and this mixture is dispersed in 50 parts of water containing 2 parts of mannitan mono-oleate, This mixture is run through a colloid mill to form an emulsion.

When using glycerol modified urea-formaldehyde resins, the resin was dissolved in a tolueneacetone mixture and then processed as above to form an emulsion.

The above synthetic non-soap surface active agents may also be classified by chemical structure as follows:

I. Water-soluble salts of mononuclear aromatic sulfonic acids containing a single long alkyl substituent of 8-20 or more carbon atoms.

Representative compounds of this type are available commercially under the trade name Nacconol NR, Keminol, Santomerse, Triton NE and Ultrawet. Nacconol NR is the sodium salt of an alkylated benzene sulfonic acid obtained by condensing a chlorinated kerosene with benzene and sulfuric acid followed by neutralization with caustic soda and including 65 sodium sulphate. Keminol is a compound of the same general type in which phenol is substituted for the benzene. Santomerse is an alkylated diphenyl sulfonic anemone acid. Triton NE is an alkyl-aryl ether sulfonate in which the sulfonic acid radical is attached to the aryl nucleus and the alkyl group contains about 12 carbon atoms. These solutions are sold commercially as a 40% product, the remainder usually consisting of sodium sulfate or other water-soluble inorganic salt. Ultrawet is also a monosodium benzene sulfonate containing an alkyl radical of -12 carbon atoms, but this material is 1sold as a 100% product and therefore contains no added sa t.

II. Esters of sulfonated carboxylic acids with a single higher aliphatic alcohol and esters of a single higher fatty acid with short-chain sulfonated alcohols. Typical examples and their tradenames are the following:

Disodium monolauryl sulfosuccinate, "Aerosol NAL" Disodium monooleyl sulfosuccinate, Aerosol NAO Sodium lauryl sulfoacetate, Nacconol LAL Sodium stearyl sulfopropionate, Igepon AP Trisodium monostearyl sulfotricarballylate.

III. Sulfonated higher primary aliphatic alcohols of 16-20 carbon atoms and sulfonated higher aliphatic hydrocarbons of 8-20 or more carbon atoms containing the sulfonate group near the end of the chain, e. g. Gardinol" and Duponol MP 189.

IV. Sulfonated amides of higher fatty acids containing at least 8 carbon atoms and the corresponding higher alkyl amides of sulfonated carboxylic acids containing at least 8 carbon atoms in the amide radical, such as the stearic acid amide of taurine (Igepon T), N-octadecyl disodium sulfosuccinamate, and N-octadecyl (N-1,2-dicarboxyethyl) tetrasodium sulfosuccinamate.

V. Unsulfonated amides and esters of higher fatty acids with polyamines and polyhydroxy polyamines, e. g. Ninol 737, which is a mixed fatty acid alkylol amine condensation product wherein the fatty acid contains 12 carbon atoms.

VI. Sodium, isopropyl and butyl naphthalene sulfonates, as sodium dioctyl sulfosuccinate (sold commercially as Aerosol OT), tri(2-ethyl butyl) sodium sulfotricarballylate (sold as Nekal NS) and higher secondary alcohol sulfates (sold as Tergitol"), which contain two relatively long alkyl groups.

All the parts and percentages given in this specification are by weight.

The present invention is a continuationdn-part of application Ser. No. 405,659 filed August 6, 1941, and application Ser. No. 566,241 filed December 1, 1944, now Patent No. 2,588,264 issued March 4, 1952.

The present application is also a continuation-in-part of application Ser. No. 792,617 filed December 18, 1947, now Patent No. 2,587,637.

Application Ser. No. 792,617 relates to a slow dissolving detergent in which the synthetic detergent and the soap will slowly dissolve at substantially the same rate.

Application Ser. No. 566,241 relates to a sodium soap detergent which will have a high detergent property in hard water and in salt water.

The present application relates to a foamless or a nonsudsing soap which is particularly useful in washing machines and for similar purposes where it is desired to limit the amount of foam or suds formed.

Since certain changes may be made in the above detergent composition and difierent embodiments of the invention could be made without departing from the scope thereof, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

What is claimed is:

1. A substantially foamless and substantially nonsudsing detergent composition comprising by weight 20 parts of the fatty acid (C9 to C20) ester of an ethylene oxide condensation product of a hexitol, 80 parts of sodium stearate and /2 part of emulsified ethyl cellulose having between about 2 and 4 ethoxy groups per glucose residue.

2. A substantially foamless and substantially non-sudsing detergent composition comprising by weight: g

3. A substantially foamless and substantially non-sudsing soap composition comprising by weight:

Per cent Sodium soap 50 to An aromatic polyethylene ether sulfate /2 to 2 An anhydro polyhydroxy compound high molecular weight fatty acid ester having from 6 to 36 CHzO groups and having from 9 to 20 carbon atoms in the fatty acid residue Emulsified ethyl cellulose having between about 2 and 4 ethoxy groups per glucose residue A to 2 4. A substantially foamless, non-sudsing detergent composit on comprising A to 2% emulsified ethyl cellulose having between about 2 and 4 ethoxy groups per glucose residue, 10 to 50% anhydro polyhydi'oxy compound high molecular weight fatty acid ester having from 6 to 36 CHzO groups and having from 9 to 20 carbon atoms in the fatty acid residue, 50 to 80% sodium soap. 5. A sudless composite detergent for mechanical washing and laundering operations comprising 70 to of a sodium high molecular weight fatty acid soap, 5 to 25% of a non-ionic organic surface active agent consisting of high molecular weight aliphatic acid esters of anhydro-hexitol ethylene oxide condensates, /2% to 2% of an anionic non-soap synthetic organic detergent and O.1 to 1% of emulsified water-insoluble ethyl cellulose having 2 to 4 ethoxy groups per glucose residue.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,085,706 Schoeller et al. June 29, 1937 2,085,733 Bird July 6, 1937 2,184,171 Sponsel et al. Dec. 19, 1939 2,202,741 Maxwell May 28, 1940 2,226,075 Rowe Dec. 24, 1940 2,301,481 Trowell Nov. 10, 1942 2,332,121 Trowell Oct. 19, 1943 2,356,168 Mabley Aug. 24, 1944 2,383,610 Morgan Aug. 28, 1945 2,407,647 Bodman Sept. 17, 1946 2,438,169 Hoyt Mar. 23, 1948 FOREIGN PATENTS Number Country Dat 211,294 Great Britain Feb. 21, 1924 340,232 Great Britain Dec. 17, 1930 423,238 Great Britain Ian. 29, 1935 884,116 France Aug. 3, 1943 OTHER REFERENCES Lorand, article in Ind. and En Che 1 vol. 30, No. 5. g m my 1938 Hercules, publication on Ethyl Cellulose, 1944, Properties and Uses. t 0Spans and Tweens, Atlas Powder Company publica- 

5. A SUDLESS COMPOSITE DETERGENT FOR MECHANICAL WASHING AND LAUNDERING OPERATIONS COMPRISING 70 TO 90% OF A SODIUM HIGH MOLECULAR WEIGHT FATTY ACID SOAP, 5 TO 25% OF A NON-IONIC ORGANIC SURFACE ACTIVE AGENT CONSISTING OF HIGH MOLECULAR WEIGHT ALIPHATIC ACID ESTERS OF ANHYDRO-HEXITOL ETHYLENE OXIDE CONDENSATES, 1/2% TO 2% OF AN ANIONIC NON-SOAP SYNTHETIC ORGANIC DETERGENT AND 0.1 TO 1% OF EMULSIFIED WATER-INSOLUBLE ETHYL CELLULOSE HAVING 2 TO 4 ETHOXY GROUPS PER GLUCOSE RESIDUE. 